Condensation products of pentaerythrityltetramine with betadiketones and beta-hydroxy methylene ketones



Patented Feb. 22, 1949 UNITED STATES PATENT OFFICE CONDENSATION PRODUCTSF PENTA- ERYTHRITYLTETRAMINE' WITH BETA- DIKETONES AND BETA-HYDROXYMETHYLENE KETON ES No Drawing. Application April 30, 1947, Serial No.745,112

Claims. 1

This invention relates to new chemical compounds and more particularlyto condensation products of pentaerythrityltetramine with betadiketonesand beta-hydroxy methylene ketones.

It is known that many organic products tend to oxidize and deterioratein the presence of oxygen. Frequently, such organic products be comecontaminated with, or come into contact with, metals and metal compoundswhich are active to catalyze the oxidation and deterioration of suchorganic products.

It has been proposed to condense various amines with certain ketones andaldehydes to produce compounds of the Schiffs base type which areeffective to varying degrees in inhibiting the oxidation anddeterioration of organic products. Some of such compounds are effectiveto inhibit oxidation and deterioration of the organic products in thepresence of oxygen and in the absence of catalytically active metals andtheir compounds but are substantially ineifective in the presence ofsuch catalytically active metals. Other compounds of the Schiffs basetype, particularly those derived from certain diamines and ortho-hydroxyaromatic aldehydes, as disclosed in Patent 2,181,121 to Downing et al.,are eifective to overcome the catalytic effect of copper and itscompounds and are known as copper deactivators or metal deactivators.Generally, such metal deactivators are effective to deactivate only oneor two metals and, hence, are of rather limited usefulness becauseorganic products frequently come into contact with a number of differentcatalytically active metals.

It is an object of the present invention to provide new chemicalcompounds. Another object is to provide new chemical compounds of theSchiffs base type which are the condensation products of apentaerythrityltetramine with a beta diketone or a hydroxy methyleneketone. A further object is to provide chemical compounds of the Schiffsbase type which are particularly effective for suppressing the catalyticactivity of most of the metals with which oxidizable organic productsare ordinarily brought into contact. Other objects are to advance theart. Still other objects Will appear hereinafter.

The above and other objects of our invention may be accomplished byproviding compounds of the formula where each of X and Y represents amember of the group consisting of hydrogen and alkyl, aralkyl and arylradicals and Z represents a member of the group consisting of alkyl,aralkyl and aryl groups. We have found that such compounds may bereadily prepared by the condensation of one mol ofpentaerythrityltetramine with four mols of beta diketone whereby one ofthe carbonyl groups condenses with the primary amino group and the othercarbonyl group is converted to a hydroxy methylene group. The compoundsmay also be obtained by condensing the amine with a beta-(hydroxy-methylene) ke'tone in place of the beta diketone. In general,such compounds are efiective to suppress the catalytic action ofvanadium, chromium, inanganese, iron, cobalt, nickel and copper andtheir catalytically active compounds on the oxidation of oxidizableorganic products. These compounds are unusual in this respect since mostmetal deactivators are efiective to suppress the catalytic activity ofonly one or two of such metals. I

The beta diketones, employed for producing our compounds, may berepresented by the formula wherein each of X and Y represents hydrogenor an alkyl, aralkyl, or aryl radical and Z represents an alkyl,aralkyl, or aryl radical. Preferably, Y represents hydrogen and X and Zrepresent hydrocarbon radicals and particularly alkyl radicals. Theresulting preferred compounds are particularly effective for overcomingthe catalytical activity of vanadium, chromium, iron, cobalt, nickel,copper, manganese and their compounds. Of these, tetra- (acetylacetone)pentaerythrityltetramine is the most effective and it is preferred.Other desirable compounds are tetra- (propionylacetone)pentaerythrityltetramine derived from propionylacetone and tetra-(benzoylacetone) pentaerythrityltetramine derived from benzoylacetone.

In place of the beta diketones, we may employ the corresponding beta-(hydroxy-methylene) ketones which may be represented by the formula areParticularly desirable beta- (hydroxymethylene) ketones are hydroxymethylene acetone and hydroxy methylene camphor which form tetra-(hydroxy-methylene acetone) pentaerythrityltetramine and tetra-(hydroxy-methylene camphor) pentaerythrityltetramine, respectively.

The ketones which may be employed to produce our novel compounds maycontain halogens, nitro groups, or groups such as wherein M is asalt-forming group or element such as ammonium, lithium, sodium,potassium, and magnesium.

The compounds of our invention include salts wherein the hydrogen atomsof the hydroxy groups are replaced by metals or other suitable cationssuch as lithium, sodium, potassium, magnesium, calcium, strontium,barium, zinc, cadmium, tin, ammonium and tetra-alk l ammonium. Some ofsuch salts such as those of the alkali metals are water-soluble and areparticularly suitable for use in aqueous systems.

The compounds of this invention are light buff colored products and aregenerally crystalline and colorless when pure. Many are soluble in waterand. all form water-soluble salts and. are soluble in alcohols. They aresufficiently soluble in hydrocarbons, such as gasoline, lubricating oilsand the like and in rubber so that they may be dissolved therein in anamount sufficient to protect such products against the catalytic actionof metals. These compounds may be readily prepared by mixing the amineand the beta diketone or beta-(hydroxy-methylene) ketone at roomtemperatures. Their preparation is usually facilitated by carrying outthe reaction in a solvent, such as water, dilute aqueous alkali,methanol, alcohol and the like. The reaction is exothermic and hence itwill generally be desirable to add one of the reactants gradually to theother, employing cooling if desired.

As illustrative of such a preparation, tetraamount of metal catalystpresent in the organic materials. Generally, the compounds will be addedin an amount equal to about 5 to about 10 times the amount of catalyticmetal present.

In order to illustrate the desirable properties When disalicylalpropylenediamine was tested in the same manner as that described above,it was found that while it was effective to deactivate copper, it Wasineffective to deactivate chromium or nickel and actually increased thepro-oxidant eifects of manganese, iron and cobalt. This is illustrativeof the effects obtained with Schifis base type compounds heretoforeproposed as metal deactivators as in Patents 2,181,121, 2,181,122,2,255,597, 2,284,267, 2,285,259 and 2,285,260.

It will thus be apparent that, by our invention, we have provided aclass of new chemical compounds which can be readily prepared. Thesecompounds have novel properties which render them useful and valuable inapplications where related compounds of the prior art are notapplicable.

This is a continuation-in-part of our copending application Serial No.625,686, filed October 30, 1945, now abandoned.

We claim:

1. A compound of the formula wherein each of X and Y represents a memberof the group consisting of hydrogen and hydrocarbon radicals and Zrepresents a hydrocarbon group.

'2. A compound of the formula HO?=CH(|3=NOH2 o X Z )4 wherein Xrepresents a hydrocarbon radical and Z represents an alkyl radical.

given EXAMPLE To a cracked gasoline which had been completely refinedbut which was otherwise untreated with chemical agents, such as dyes,antiknocks and antioxidants, and which had an induction period of 120minutes, was added 0.0025% of 4-(n-butylamino) -phenol, an antioxidant,whereby the inductionperiod was raised to 380 minutes. To differentsamples of this gasoline, there was added gasoline soluble salts of thecatalytic element (indicated by the chemical symbols of the element) inthe indicated concentrations in parts per million of the element. Toportions of these samples, there was added 0.005% by weight oftetra-(acetylacetone) pentaerythrityltetramine. The induction periods ofthe various samples were then determined by the Voorhees- Eisingerinduction method described in J. I. E. C. 25, 397 (1933). The resultsare given in the following table:

3. Tetra-(acetylacetone) pentaerythrityltetramine having the formulawherein each of X and Y represents a hydrocarbon radical and Zrepresents an alkyl radical.

5. A compound of the formula wherein Z represents an alkyl radical.

CHARLES J. PEDE-RSEN. FREDERICK BAXTER DOWNING.

REFERENCES CITED The following references are of record in the file ofthis patent:

2,285,260 Downing et al. June 2, 1942

